3.

RATE LAWS AND

STOICHIOMETRY

In Chapter 2 we saw that if we had –rA as a

function of X, [–rA= f(X)] we could size many
reactors and reactor sequences and systems.

How do we obtain –rA = f(X)?

We do this in two steps
1. Part 1 Rate Law – Find the rate as a function
of concentration,

2. Part 2 Stoichiometry – Find the

concentration as a function of conversion

Combine Part 1 and Part 2 to get

Part 2: Stoichiometry

Stoichiometric Table for A Batch System

1
Reaction: aA  bB  cC  dD
For A is the limiting reactant:
b c d
A B C D
a a a

Species Initially Change Remaining

(mol) (mol) (mol)
A NA0  N A0 X  N A  N A 0 1  X 
B NB0 b  b 
 N A0 X  N B  N A0  Θ B  X 
a  a 
C NC0 c  c 
N A0 X  N C  N A0  Θ C  X 
a  a 
D ND0 d  d 
N A0 X  N D  N A0  Θ D  X 
a  a 
I (inerts) NI0 ─ N I  N A0Θ I
_____ ___________________
Totals NT0 N T  N T 0  δN A 0 X
d c b
δ    1
a a a
N i0 Ci 0 yi0
Θi   
N A0 C A0 y A0
In general:
N j  N A 0 Θ j  ν j X 
j = stoichiometric coefficients j → negative for
reactant and positive for product. Thus: A = -1;
B= b/a; C= c/a; D= d/a; and I= 0.
N
Concentration of i for a batch system: Ci  i
V
2
 N A N A 0 1  X 
e.g.: CA  
V V

Constant-Volume Reaction System (= constant

density reaction system):
1. Liquid phase reaction
2. Gas phase reaction in a constant volume batch
reactor
3. Isothermal-isobaric gas phase reaction where
the number of moles of product equals the
number of moles of reactant, and compressibility
factors of reactants are the same as those of
products.

For a constant volume reaction system, V=V0,

thus:
C j  C A 0 Θ j  ν jX 

Problem 3.4
Write the rate law for the elementary liquid
phase reaction.

solely in terms of conversion. The feed to the

batch reactor is equal molar A and B with CA0 =
2 mol/L and kA= 0,01 (L/mol)4/s.
Stoichiometric Table for A Flow System
b c d
A B C D
a a a
3
Species Initially Change Remaining
(mol/time) (mol/time) (mol/time)
A FA0  FA 0 X  FA  FA 0 1  X 
B FB0 b  b 
 FA 0X  FB  FA 0  Θ B  X 
a  a 
C FC0 c  c 
FA0X  FC  FA 0  ΘC  X 
a  a 
D FD0 d  d 
FA0X  FD  FA 0  Θ D  X 
a  a 
I FI0 ─ FI = FI0 = FA0ΘI
(inerts)
________ _____________________
Totals FT0 d c b 
FT  FT 0      1FA 0X
a a a 
FT  FT 0  δFA 0X
Notice:
Fi 0 Ci0 v 0 Ci0 yi0
Θi    
FA 0 C A 0 v 0 C A 0 y A 0
And in general:
Fj  FA 0 Θ j  ν jX 
F
Concentration of i for a flow system: Ci  i
v
F F 1  X 
e.g.: CA  A  A0
v v

For liquids, volume change with reaction is

negligible when no phase changes are taking
place. Cosequently,
v  v 0  constant
4
and
C j  C A 0 Θ j  ν jX 

However, for gas phase reactions, the volumetric

flow rate most often changes during the course
of the reaction due to several reasons, such as:
1. A change in the total number of moles
2. A change in temperature
3. A change in pressure (such as due to
pressure drop in a PFR or PBR)

Volume Change with Reaction

Variation of V in a batch system or v in a flow
system during reaction.

Gas phase batch system:

PV  ZN T RT
where:
T = temperature, K
P = total pressure, atm
Z = compressibility factor
R = universal gas constant = 0,08206
L.atm/gmol.K
V = volume of a batch system, L
NT = total mol of gas in the system, gmol

At t=0: P0 V0  Z 0 N T 0 RT0

5
  P0  T  Z  N T 
Thus: V  V0     
 P  T0  Z0  N T 0 

From stoichiometric table:

N T  N T 0  δN A 0 X
or:
NT N
 1  δ A 0 X  1  δy A 0 X
NT0 N T0
where:
yA0 = mole fraction of A at t =0
If all the species in the generalized reaction are
in the gas phase, then:
d c b
δ    1
a a a
Let:

NT
ε  1  δy A 0
N T 0 X 1
Combine with the previous equation, we have:
 P0  T  Z 
V  V0    1  εX 
 P  T0  Z 0 
For Z0  Z,
 P  T 
V  V0  0  1  εX 
 P  T0 
Concentration of gas j for a variable volume
batch reaction as a function of X:
6
 Nj N A 0 Θ j  ν jX 
Cj  
V  P0  T 
V0 1  εX   
 P  T0 
Θ j  ν jX  P  T0 
 C A0  
1  εX   P0  T 

Gas phase flow system:

Pv  ZFT RT
For a negligible change in Z,
 FT  P0  T 
v  v 0    
 FT 0  P  T0 
From stoichiometric table:
FT  FT 0  δFA 0 X
or:
FT FA 0
1 δ X  1  δy A 0 X  1  ε X
FT 0 FT 0
Then:
 P  T   P  T 
v  v 0 1  δy A 0 X  0    v 0 1  εX  0  
 P  T0   P  T0 

Concentration of j in a flow system as a function

of X:

7
 Fj FA 0 Θ j  ν jX 
Cj  
v  P0  T 
v 0 1  εX   
 P  T0 
Θ j  ν jX  P  T0 
 CA0  
1  εX   P0  T 

Equation of Cj for a flow system = equation of

Cj for a batch system.

Problem 3.7.: Determining Cj = hj(X) for a

Gas Phase Reaction
A mixture of 28% SO2 and 72% air is charged to
a flow reactor. Reaction:
2SO2 + O2 2SO3
P constant = 1485 kPa, and T constant = 227C.
Set up a stoichiometric table. Express

Let the reaction proceed in a PBR using catalyst

V2O5/silica gel. The rate of reaction is (Hill,
1977, p. 509):
k1CSO 2 C O 2  k 2 CSO3 C1O/2
 rSO 2  2

C1SO
/2
2

8
 k1C A C B  k 2 C C C1B/2
 rA 
C1A/2

  1  X    0,54  0,5X  
k1  0,1   0,1  
 1  0,14X    1  0,14X  
1/2
  X    0,54  0,5X  
 k 2  0,1   0,1  
 1  0,14X    1  0,14X  
 1/2
  1 X 
 0,1  
 1  0,14X  

We obtain:  rA  f X 
Calculating the equilibrium conversion for
gas phase reaction
Problem 3.8.:
Consider the following elementary reaction with
KC = 20 L/mol and CA0 = 0.2 mol/L. Pure A fed.
Calculate the equilibrium conversion, Xe, for
both a constant volume batch reactor and a flow
reactor.

Solution
9
At equilibrium

Stoichiometry

Constant volume batch reactor

Species Initial Change Remaining

A NA0 -NA0X NA = NA0(1-X)
B 0 +NA0X/2 NB = NA0X/2
NT0 = NT = NA0 -
NA0 NA0X/2

Constant Volume V = V0

10
Solving
Xe = 0,7

Flow

Species Fed Change Remaining

A FA0 -FA0X FA = FA0(1-X)
B 0 +FA0X/2 FB = FA0X/2
FT = FA0 -
FT0 = FA0
FA0X/2

11
Xe = 0,757

Expressing Concentrations in Terms Other

Than Conversion
For a gas phase in a flow system with negligible
change in Z:
 FT  P0  T   FT  P0  T 
v  v 0         
 FT 0  P  T0   C T 0  P  T0 
where:
FT 0 P0
CT0  
v 0 Z 0 RT0
Concentration of gas j in a flow system:
Fj  Fj  P  T0 
C j   CT 0    
v  FT  P0  T 
12
with
FT   Fj
j is the specieses in the system including inert.

Problem 3.9.
The following elementary gas reaction is carried
out in a isothermal-isobaric PFR:
N2O4 2NO2
A 2B
The feed is pure A. Express the rate law and
mole balances in terms of the molar flow rates.

Solution:
dFA  P0 
 rA  k A  
dV  Z0 RT0 
 F 1  P  F 
2
 A   0  B  

 FA  FB K C  Z0 RT0  FA  FB  

dFB  P0 
 rB  2rA  2k A  
dV  Z0 RT0 
 F 1  P  F 
2
 A   0  B  

 FA  FB K C  Z0 RT0  FA  FB  

13